第一性原理研究Nb、Sn、Cu、Fe和Cr对Zr (0001)晶面抗疖状腐蚀性能的影响

doi:10.19596/j.cnki.1001-246x.8328

摘要/Abstract

摘要：

采用密度泛函理论研究Nb、Sn、Cu、Fe和Cr 5种合金元素对氧在Zr(0001)晶面吸附能的影响, 发现Nb、Sn和Cu会促进氧在Zr(0001)晶面吸附, Fe和Cr对氧吸附的影响因吸附的位置不同而存在差异。研究5种合金元素对氧化后Zr(0001)晶面化学键的破坏情况, 发现Nb对Zr(0001)晶面破坏程度最小而且可以迅速复原, Sn可以使(0001)晶面相邻的两个化学键都变长, 对晶面的破坏性大。最后讨论5种合金元素在Zr(0001)晶面的偏聚能, 发现Sn、Fe和Cr偏聚能为负值, 容易偏聚到Zr(0001)晶面, 而Nb和Cu偏聚能为正值, 不易在Zr(0001)晶面偏聚。综合以上分析, Nb可以促进氧在Zr(0001)晶面的吸附行为, 氧化后(0001)晶面可以快速复原, 从而阻碍其他氧原子进入, 抑制疖状腐蚀的发生。Sn容易偏聚到Zr(0001)晶面, 可以促进氧在Zr(0001)晶面吸附, 氧化后会造成Zr(0001)晶面较大的破坏, 促进氧进入Zr(0001)晶面, 促进疖状腐蚀的发生。

关键词: 锆合金, 疖状腐蚀, 合金元素, 密度泛函理论

Abstract:

Density functional theory is used to study the influence of Nb, Sn, Cu, Fe and Cr on the adsorption energy of oxygen on crystal face of Zr (0001).It was found that Nb, Sn and Cu promote adsorption of oxygen on the surface, and the influence of Fe and Cr on oxygen adsorption is different due to the location of the oxygen adsorption.Secondly, we studied destruction of microtexture on the oxidized surface by the alloying elements.It was found that the damage of Nb to the crystal face of Zr (0001) is the least and it can be recovered quickly, while Sn makes two chemical bonds longer, so the damage to the crystal face is great.Finally, the segregation of Sn, Fe and Cr to surface is exothermic, while the segregation of Nb and Cu to surface is endothermic.We conclude that Nb promotes the adsorption of oxygen on Zr (0001) crystal face, and the surface recovers quickly after oxidation, which preventing the entry of oxygen atoms and inhibiting the occurrence of nodular corrosion.Sn segregateds on Zr (0001) crystal face easily, which promotes the adsorption of oxygen on Zr (0001) crystal face, and causes the microstructure distortion of Zr (0001) crystal face.After oxidation, the crystal surface of Zr (0001) is damaged greatly, which promotes the rapid entry of oxygen and the occurrence of nodular corrosion.

Key words: zirconium alloys, nodular corrosion, alloying elements, density functional theory

高慧, 杨在发, 赵敬芬, 袁慧敏, 刘志娥, 赵显. 第一性原理研究Nb、Sn、Cu、Fe和Cr对Zr (0001)晶面抗疖状腐蚀性能的影响[J]. 计算物理, 2022, 39(1): 101-108.

Hui GAO, Zaifa YANG, Jingfen ZHAO, Huimin YUAN, Zhie LIU, Xian ZHAO. Effect of Nb, Sn, Cu, Fe and Cr on Zr (0001) Surface Nodular Corrosion Resistance: First Principles Study[J]. Chinese Journal of Computational Physics, 2022, 39(1): 101-108.

图/表 5

图1 氧原子在Zr(0001)晶面吸附俯视图(a)氧原子吸附在top位；(b)氧原子吸附在hcp位；(c)氧原子吸附在fcc位 (紫色表示表层(第一层)Zr原子，黄色表示第二层Zr原子。红色的表示不同吸附位的氧原子，绿色的表示合金元素。黑色线表示超晶胞边界，圆棍表示原子间的化学键。)

Fig.1 Top view of atmoic structure of Zr (0001) crystal face (a) Oxygen atom is at the top position; (b) Oxygen atom is at the hcp position; (c) Oxygen atom is at the fcc position (The purple and yellow spheres represent Zr atoms in the first layer and the second layer, respectively. The red spheres represent oxygen atoms and the green ones represent alloying elements. The black line represents boundary of supercell and the sticks indicate bonds between atoms.)

表1 Zr(0001)晶面和含Nb、Sn、Cu、Fe、Cr合金元素的Zr(0001)晶面的氧原子吸附能(Eb/eV)

Table 1 Adsorption energies of oxygen on Zr(0001) crystal face and Zr(0001) crystal face with Nb、Sn、Cu、Fe、Cr(Eb/eV)

position	pure-Zr	Nb	Sn	Cu	Fe	Cr
top	-7.46	-8.02	-3.22	-4.54	-5.50	-6.54
hcp	-10.75	-12.80	-12.21	-12.32	-8.31	-11.69
fcc	-11.13	-13.18	-11.94	-12.27	-12.07	-9.14

表2 含合金元素氧化后Zr(0001)晶面(三层)化学键键长(单位：nm)

Table 2 Bond lengths of oxidation Zr(0001) crystal face containing alloying elements (in the top three layers) (in nm)

	Cu	Sn	Nb	Fe	Cr
The first layer	Cu-Zr; Zr-Zr	Sn-Zr; Zr-Zr	Nb-Zr; Zr-Zr	Fe-Zr; Zr-Zr	Cr-Zr; Zr-Zr
The first layer	0.311;0.327	0.334;0.326	0.320;0.322	0.392;0.306	0.321;0.313
The second layer	Zr-Zr
The second layer	0.323;0.324	0.325;0.326	0.324;0.321	0.325;0.322	0.331;0.322
The third layer	Zr-Zr
The third layer	0.323;0.325	0.326;0.325	0.324;0.324	0.318;0.320	0.325;0.328

图2 含合金元素氧化后Zr(0001)晶面三层内最近邻两个化学键(X-Zr (X=Nb、Sn、Cu、Fe、Cr), Zr-Zr)与完整的晶体两个锆之间的键长差值(单位为nm)

Fig.2 Difference of bond length between the two nearest chemical bonds (X-Zr (X=Nb, Sn, Cu, Fe, Cr), Zr-Zr) and the two zirconium in a perfect crystal after the oxidation of Zr(0001)crystal surface (unit in nm)

表3 Nb、Sn、Cu、Fe、Cr在Zr(0001)晶面的偏聚能(Es/eV)

Table 3 Partial poly energy of Nb, Sn, Cu, Fe and Cr on the surface of Zr(0001)(Es/eV)

Cu	Sn	Nb	Fe	Cr
1.69	-0.87	0.16	-0.78	-0.32

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